Cosmetic or pharmaceutical preparations which comprise enaminotriazines as light protection agents, and novel enaminotriazines

ABSTRACT

The invention relates to the use of enaminotriazines of the formula I  
                 
 
in which the radicals Y, independently of one another, are hydrogen, an optionally substituted aliphatic, cycloaliphatic, araliphatic or aromatic radical having in each case up to 18 carbon atoms, the radicals X are identical or different, where at least one of the radicals X is the ethenyl radical of the formula II  
                 
and X may also have the meanings of Y, and where in the formula II the radicals R are identical or different and are cyano, optionally esterified carboxyl, substituted carbonyl, optionally substituted aminocarbonyl, optionally esterified sulfo, substituted sulfonyl or optionally esterified phosphono, and where two adjacent radicals R may optionally form a ring and the radicals R′ are identical or different and are hydrogen, an optionally substituted aliphatic, cycloaliphatic or aromatic radical having in each case up to 18 carbon atoms, as UV filters in cosmetic or pharmaceutical preparations for protecting human skin or human hair against solar rays, alone or together with compounds which absorb in the UV region and which are known per se for cosmetic preparations.

The invention relates to the use of substituted enaminotriazines as UVfilters alone or together with further UV filters in cosmetic andpharmaceutical preparations, and to novel enaminotriazines.

The light protection agents used in cosmetic and pharmaceuticalpreparations have the task of preventing, or at least reducing theconsequences of, harmful effects of sunlight on the human skin. Inaddition, these light protection agents also, however, serve to protectfurther ingredients against decomposition or degradation by UVradiation. In hair cosmetic formulations, the aim is to reduce damage tothe keratin fibers by UV rays.

The sunlight which reaches the surface of the earth has a content ofUV-B radiation (280 to 320 nm) and of UV-A radiation (>320 nm), whichdirectly border the visible light region. The effect on the human skinbecomes evident, particularly in the case of UV-B radiation, fromsunburn. Accordingly, the industry offers a relatively large number ofsubstances which absorb UV-B radiation and thus prevent sunburn.

Dermatological investigations have now shown that UV-A radiation is alsoperfectly capable of causing skin damage and allergies, by, for example,damaging the keratin or elastin. This reduces the elasticity andwater-storability of the skin, i.e. the skin becomes less supple andtends to form wrinkles. The noticeably high incidence of skin cancer inareas of strong solar irradiation shows that damage to the geneticinformation in the cells is evidently also caused by sunlight,specifically by UV-A radiation. All of these findings therefore suggestthe need to develop efficient filter substances for the UV-A and UV-Bregions.

There is a growing need for light protection agents for cosmetic andpharmaceutical preparations whose absorption maxima should be in therange from about 280 to 380 nm. In order to achieve the desired effectusing the lowest possible amount, light protection agents of this typeshould additionally have a high specific absorbance. Furthermore, lightprotection agents for cosmetic preparations must also satisfy a largenumber of further requirements, for example good ability to beformulated in cosmetic preparations, high stability of the emulsionsprepared therewith, toxicological acceptability, and low intrinsic odorand low intrinsic color.

Although a large number of UV light protection agents are already known,the combination of the properties of high absorbance in the UV-A and/orUV-B region and photostability has been realized only to anunsatisfactory degree. There is therefore a need for UV filters whichrealize these requirements to a particularly high degree.

It is an object of the invention to provide novel light protectionagents which satisfy these requirements. We have found that this objectis achieved by the use of enaminotriazines of the formula I

in which the radicals Y, independently of one another, are hydrogen, anoptionally substituted aliphatic, cycloaliphatic, araliphatic oraromatic radical having in each case up to 18 carbon atoms, the radicalsX are identical or different, where at least one of the radicals X isthe ethenyl radical of the formula II

and X may also be hydrogen, and where in the formula II, the radicals Rare identical or different and are cyano, optionally esterifiedcarboxyl, substituted carbonyl, optionally substituted aminocarbonyl,optionally esterified sulfo, substituted sulfonyl or optionallyesterified phosphono (i.e. the radical (HO)₂OP—), and where two adjacentradicals R can optionally form a ring, and the radicals R′ are identicalor different and are hydrogen, an optionally substituted aliphatic,cycloaliphatic or aromatic radical having in each case up to 18 carbonatoms, as UV filters in cosmetic or pharmaceutical preparations forprotecting human skin or human hair against solar rays, alone ortogether with compounds which absorb in the UV region and which areknown per se for cosmetic preparations.

In this connection, preference is given to the use of compounds of theformula I in which Y is hydrogen and one or more of the radicals X arean ethenyl radical of the formula IIa

in which the radicals R¹ and R² are identical or different and are—COOR⁴, —COR⁴, —CON(R⁴)₂, —CN, —SO₂R⁴, —SO₂OR⁴ or —PO(OR⁴)₂, where theradicals R⁴, independently of one another, are hydrogen; an aliphatic,cycloaliphatic, araliphatic or aromatic radical, each of which may beoptionally substituted, and where adjacent radicals R¹ and R² mayoptionally form a ring and R³ is hydrogen or an aliphatic,cycloaliphatic, araliphatic or aromatic radical, each of which may besubstituted.

Particular preference is given to compounds of the formula I in which R³is hydrogen, R¹ and R² are identical or different and —COOR⁵, —COR⁵ or—CN, where R⁵ is an aliphatic or optionally substituted aromatic radicalhaving up to 18 carbon atoms.

The invention equally relates to cosmetic or pharmaceutical preparationscomprising light protection agents for protecting human skin or humanhair against solar rays, alone or together with compounds which absorbin the UV region and which are known per se for cosmetic preparationsand which comprise, as essential UV filters, effective amounts ofenaminotriazines of the formula I

in which the radicals Y, independently of one another, are hydrogen, anoptionally substituted aliphatic, cycloaliphatic, araliphatic oraromatic radical having in each case up to 18 carbon atoms, the radicalsX are identical or different, where at least one of the radicals X isthe ethenyl radical of the formula II

and X may also be hydrogen, and where in the formula II the radicals Rare identical or different and are cyano, optionally esterifiedcarboxyl, substituted carbonyl, optionally substituted aminocarbonyl,optionally esterified sulfo, substituted sulfonyl or optionallyesterified phosphono, and where two adjacent radicals R may optionallyform a ring, and the radicals R′ are identical or different and arehydrogen, an optionally substituted aliphatic, cycloaliphatic oraromatic radical having in each case up to 18 carbon atoms.

Finally, the invention also relates to tris(ethenylamino)triazines ofthe formula III as novel compounds

in which the radicals R¹ and R² are identical or different and are—COOR⁴, —COR⁴, —CON(R⁴)₂, —CN, —SO₂R⁴, —SO₂OR⁴ or —PO(OR⁴)₂, where theradicals R⁴, independently of one another, are hydrogen, an aliphatic,cycloaliphatic, araliphatic or aromatic radical, each of which may beoptionally substituted, and where two adjacent radicals R may optionallyform a ring and R³ is hydrogen or an aliphatic, cycloaliphatic,araliphatic or aromatic radical, each of which may be substituted.

In all of the abovementioned compounds, the enamine group may be in theE or Z configuration.

Enaminotriazines are known from a number of literature sources, e.g.from Hashida, Y; Imai, A.; Sekiguchi, S; J. Heterocyclic Chem. 1989, 26,901-5, WO 99/02495 and WO 98/47893.

In addition, Kreutzberger, A; Grundmann, C; J Org. Chem. 1961, 4,1121-1126 has already described enamino(hexahydro)triazines. In none ofthese literature sources is the use of these compounds as lightprotection agents in cosmetic preparations disclosed or suggested.

Finally, aromatics carrying enamino substituents are known as lightprotection agents in cosmetic preparations from EP-A 895 776 and EP-A852 137. The latter specification also gives the general informationthat the aromatic radical may also be a heteroaromatic.

However, it could not be deduced from these literature sources that theenaminotriazines to be used according to the invention are characterizedby their particularly advantageous properties, such as very highabsorbance and high photostability.

Particular preference is given to the use of compounds of the formula Iin which R³ is hydrogen and R¹ and R², independently of one another, areCN, COOR⁴ and COR⁴, where R⁴ is identical or different open-chain orbranched aliphatic or optionally substituted, aromatic radicals havingup to 8 carbon atoms.

Suitable substituents are lipophilic and also hydrophilic substituentshaving e.g. up to 20 carbon atoms. Lipophilic radicals, i.e. radicalswhich boost the solubility in oil of the compounds of the formula I,are, for example aliphatic or cycloaliphatic radicals, in particularalkyl radicals having 1 to 18 carbon atoms, alkoxy, mono- anddialkylamino, alkoxycarbonyl, mono- and dialkylaminocarbonyl, mono- anddialkylaminosulfonyl radicals, and also cyano, nitro, bromo, chloro,iodo or fluoro substituents.

Hydrophilic radicals, i.e. radicals which allow the compounds of theformula I to dissolve in water, are, for example, carboxyl and sulfoxyradicals and, in particular, salts thereof with any physiologicallycompatible cations, such as the alkaline metal salts or thetrialkylammonium salts, such as tri(hydroxyalkyl)ammonium salts or the2-methylpropan-1-ol-2-ammonium salts. Also suitable are alkylammoniumradicals having any physiologically compatible anions. Low-solubilitycompounds of the formula I can be used in micronized form in cosmeticpreparations.

Suitable alkoxy radicals are those having 1 to 12 carbon atoms,preferably having 1 to 8 carbon atoms.

Examples which may be mentioned are: methoxy isopropoxy n-propoxy1-methylpropoxy n-butoxy n-pentoxy 2-methylpropoxy 3-methylbutoxy1,1-dimethylpropoxy 2,2-dimethylpropoxy hexoxy 1-methyl-1-ethylpropoxyheptoxy octoxy 2-ethylhexoxy

Suitable mono- or dialkylamino radicals are, for example, those whichcontain alkyl radicals having 1 to 8 carbon atoms, such as methyl,n-propyl, n-butyl, 2-methylpropyl, 1,1-dimethylpropyl, hexyl, heptyl,2-ethylhexyl, isopropyl, 1-methylpropyl, n-pentyl, 3-methylbutyl,2,2-dimethylpropyl, 1-methyl-1-ethylpropyl and octyl. These radicals areequally present in the mono- and dialkylaminocarbonyl and sulfonylradicals.

The compounds of the formulae I and III to be used according to theinvention can be prepared in accordance with the equation by reacting acompound having an activated methylene group with melamine in thepresence of orthoformate according to the following scheme

by condensation in a manner known per se, where R¹ to R³ have the abovemeanings.

Examples of compounds R¹-CH₂-R² containing active methylene groups arecyanoacetic esters, cyanoacetamides, cyanoacetic acid, malonic esters,malonamides, malonic acid, acetoacetic esters, acetoacetamides,acetoacetic acid, 1,3-diketones, malodinitrile and α-cyanoketones.

Depending on how the ratio of the methylene compound (and orthoformate)to melamine is chosen, mono-, di- or trisubstitution of the melamine isachieved. Preference is given to the reaction with an at least 3-foldmolar amount, so that the trisubstituted compound is predominantlyobtained. Details of the synthesis method are given in the informationin EP-A 0 852 137.

The cosmetic and pharmaceutical preparations which comprise lightprotection agents are usually based on a carrier which comprises atleast one oil phase. However, preparations merely based on water arealso possible if compounds with hydrophilic substituents are used.Accordingly, suitable preparations are oils, oil-in-water andwater-in-oil emulsions, creams and pastes, lipcare stick compositions orgrease-free gels.

Sunscreen preparations of this type can, accordingly, be in liquid,paste or solid form, for example as water-in-oil creams, oil-in-watercreams and lotions, aerosol foam creams, gels, oils, wax pencils,powders, sprays or alcoholic-aqueous lotions.

Examples of customary oil components in cosmetics are paraffin oil,glyceryl stearate, isopropyl myristate, diisopropyl adipate,cetylstearyl 2-ethylhexanoate, hydrogenated polyisobutene, Vaseline,caprylic/capric triglycerides, microcrystalline wax, lanolin and stearicacid.

Customary cosmetic auxiliaries which may be suitable as additives are,for example, coemulsifiers, fats and waxes, stabilizers, thickeners,biogenic active ingredients, film formers, fragrances, dyes, pearlizingagents, preservatives, pigments, electrolytes (e.g. magnesium sulfate)and pH regulators. Suitable coemulsifiers are preferably known W/O andalso O/W emulsifiers such as, for example, polyglycerol esters, sorbitanesters or partially esterified glycerides. Typical examples of fats areglycerides; waxes which may be mentioned are, inter alia, beeswax,paraffin wax or microcrystalline waxes, possibly in combination withhydrophilic waxes. Stabilizers which can be used are metal salts offatty acids such as, for example, magnesium, aluminum and/or zincstearate. Suitable thickeners are, for example, crosslinked polyacrylicacids and derivatives thereof, polysaccharides, in particular xanthangum, guar guar, agar agar, alginates and tyloses, carboxymethylcelluloseand hydroxyethylcellulose and also fatty alcohols, monoglycerides andfatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone.Examples of biogenic active ingredients are plant extracts, proteinhydrolysates and vitamin complexes. Examples of customary film formersare hydrocolloids such as chitosan, microcrystalline chitosan orquaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinylacetate copolymers, polymers of the acrylic acid series, quaternarycellulose derivatives and similar compounds. Examples of suitablepreservatives are formaldehyde solution, p-hydroxybenzoate or sorbicacid. Examples of pearlizing agents are glycol distearic esters such asethylene glycol distearate, but also fatty acids and fatty acidmonoglycol esters. Dyes which can be used are the substances suitableand approved for cosmetic purposes, as listed, for example, in thepublication “Kosmetische Färbemittel” [Cosmetic Colorants] from theFarbstoffkommission der Deutschen Forschungsgemeinschaft, [DyesCommission of the German Research Society], published in Verlag Chemie,Weinheim, 1984. These dyes are normally used in concentrations of from0.001 to 0.1% by weight, based on the total mixture.

The total content of auxiliaries and additives can be from 1 to 80% byweight, preferably from 6 to 40% by weight, and the nonaqueous fraction(“active substance”) can be from 20 to 80% by weight, preferably from 30to 70% by weight, based on the compositions. The compositions can beprepared in a manner known per se, i.e. for example by hot, cold,hot-hot/cold or PIT emulsification. This is a purely mechanical process;no chemical reaction takes place.

Finally, it is also possible to co-use other substances which absorb inthe UV-A region and are known per se, provided they are stable in theoverall system of the combination of UV-B and UV-A filters to be usedaccording to the invention.

The present invention further provides cosmetic and pharmaceuticalpreparations which comprise 0.1 to 10% by weight, preferably 1 to 7% byweight, based on the total amount of the cosmetic and pharmaceuticalpreparation, of one or more compounds of the formula I together withcompounds which absorb in the UV-B region and which are known per se forcosmetic and pharmaceutical preparations, as light protection agents,where the compounds of the formula I are generally used in a lesseramount than the UB-B-absorbing compounds.

Suitable UV-B filter substances which are used in combination with thecompounds of the formula I to be used according to the invention are anyUV-B filter substances. Examples which may be mentioned are: CAS No. No.Substance (=acid) 1 4-Aminobenzoic acid 150-13-0 23-(4′-Trimethylammonium)benzylidenebornan-2-one 52793-97-2 methylsulfate3 3,3,5-Trimethylcyclohexyl salicylate 118-56-9 (homosalate) 42-Hydroxy-4-methoxybenzophenone 131-57-7 (oxybenzone) 52-Phenylbenzimidazole-5-sulfonic acid and its 27503-81-7 potassium,sodium and triethanolamine salts 63,3′-(1,4-Phenylenedimethine)bis(7,7-dimthyl- 90457-82-22-oxobicyclo[2.2.1]heptane-1-methanesulfonic acid) and its salts 7Polyethoxyethyl 4-bis(polyethoxy)aminobenzoate 113010-52-9 82-Ethylhexyl 4-dimethylaminobenzoate 21245-02-3 9 2-ethylhexylsalicylate 118-60-5 10 Isoamyl 4-methoxycinnamate 7/6/7-10-2 112-Ethylhexyl 4-methoxycinnamate 5466-77-3 122-Hydroxy-4-methoxybenzophenone-5-sulfonic 4065-45-6 acid(sulisobenzone) and the sodium salt 133-(4′-Sulfobenzylidene)bornan-2-one and salts 58030-58-6 143-(4′-Methylbenzylidene)bornan-2-one 36861-47-9 153-Benzylidenebornan-2-one 16087-24-8 161-(4′-Isopropylphenyl)-3-phenylpropane-1,3- 63260-25-9 dione 174-Isopropylbenzyl salicylate 94134-93-7 182,4,6-Trianilino(o-carbo-2′-ethylhexyl-1′-oxy)- 88122-99-01,3,5-triazine 19 3-Imidazol-4-yl-acrylic acid and its ethyl⁻ 104-98-3*ester 20 Ethyl 2-cyano-3,3-diphenylacrylate 5232-99-5 21 2′-Ethylhexyl2-cyano-3,3-diphenylacrylate 6197-30-4 22 Methyl o-aminobenzoate or:134-09-8 5-methyl-2-(1-methylethyl)-2-aminobenzoate 23 Glycerylp-aminobenzoate or: 1-glyceryl 136-44-7 4-aminobenzoate 242,2′-Dihydroxy-4-methoxybenzophenone- 131-53-3 (dioxybenzone) 252-Hydroxy-4-methoxy-4-methylbenzophenone — 1641-17-4 (Mexenone) 26Triethanolamine salicylate 2174-16-5 27 Dimethoxyphenylglyoxalic acidor: sodium 3,4-dimethoxyphenylglyoxalate 283-(4′-Sulfobenzylidene)bornan-2-one and its 56039-58-8 salts

If, on the other hand, the compound of the formula I to be usedaccording to the invention is a UV-B filter, it can of course also becombined with UV-A filters or else broadband absorbers known per se.

Examples of such UV-A and broadband absorbers are CAS No. No. Substance(=acid) 29 1,1-Bis(neopentyloxycarbonyl)-4,4-diphenyl- according1,3-butadiene to EPA 916335 30 n-Hexyl2-(4′-diethylamino-2′-hydroxybenzoyl)- 302776-68-7 benzoate 312,2′-Methylenebis[6-(2H-benzotriazol-2-yl)- 103597-45-14-(1,1,3,3-tetramethylbutyl)phenol (Tinosorb ® M) 322,2′-[6-Methoxyphenyl)-1,3,5-triazin-2,4-diyl]- 187393-00-6bis[5-[(2-ethylhexyl)oxy]phenol (Tinosorb ® S) 332-[5,6-Disulfo(1H-benzimidazol-2-yl)phenyl]-1H- 180898-37-7benzimidazole-5,6-disulfonic acid 342-(2H-1,2,3-Benzotriazol-2-yl)-4-methyl- 155633-54-86-(2-methyl-3-[1,3,3,3-tetramethyl-1-[trimethylsilyl)oxy]disiloxanyl]propyl)phenol

Finally, mention may also be made of micronized pigments such astitanium dioxide and zinc oxide.

To protect human hair from UV rays, the light protection agents of theformula I according to the invention can be incorporated into shampoos,lotions, gels or emulsions in concentrations of from 0.1 to 10% byweight, preferably from 1 to 7% by weight. The respective formulationscan be used, inter alia, for washing, coloring and for styling the hair.

The compounds to be used according to the invention are usuallycharacterized by a particularly high absorbance. Furthermore, they arereadily soluble in cosmetic oils and can be readily incorporated intocosmetic formulations. The emulsions prepared with the compounds I arecharacterized in particular by their high stability, the compounds Ithemselves by their high photostability, and the preparations preparedwith I by their pleasant feel on the skin.

The pharmaceutical use according to the invention essentially relates totopical application. Application is, for example, in the form of anointment, cream, gel, spray, solution or lotion.

EXAMPLES I. Preparation Example 1

0.1 mol of melamine, 0.3 mol of ethyl cyanoacetate and 0.3 mol oftriethyl orthoformate were heated at 120° C. for 11 h, and ethanoldistilled off. After cooling, 200 ml of ethanol were added, and theprecipitate formed was filtered off. The residue was washed withpetroleum ether and dried at 50° C. under reduced pressure. This gave29.1 g (59%) of the compound of the formula III in which R³ is hydrogen,R¹ is cyano and R² is ethyloxycarbonyl (λ_(max)=318 nm; E₁ ¹=1784)

In an analogous way, highly active compounds of the formula I areobtained if the activated methylene compounds used as starting compoundsare the following compounds:

-   -   methyl acetoacetate    -   ethyl acetoacetate    -   2-ethylhexyl acetoacetate    -   acetylacetone    -   dibenzoylmethane    -   pivaloylacetonitrile    -   dimethyl malonate    -   diethyl malonate    -   di(2-ethylhexyl) malonate    -   benzoylacetonitrile    -   benzoxazol-2-ylacetonitrile    -   benzoxazol-2-ylacetic acid    -   methyl benzoxazol-2-ylacetate    -   ethyl benzoxazol-2-ylacetate    -   2-ethylhexyl benzoxazol-2-ylacetate    -   methylcyanoacetate    -   2-ethylhexyl cyanoacetate    -   1-phenyl-1,3-butanedione    -   benzoylacetonitrile    -   malodinitrile    -   indane-1,3-dione    -   2,2-dimethyl-1,3-dioxane-4,6-dione (Meldrum's acid)    -   sulfonyldiacetonitrile    -   2-benzimidazoylacetonitrile    -   (1H-benzimidazol-2-yl)acetic acid    -   ethyl (1H-benzimidazol-2-yl)acetate    -   ethyl (1H-benzimidazol-2-yl)acetate    -   2-ethylhexyl (1H-benzimidazol-2-yl)acetate

General preparation procedure for the preparation of emulsions forcosmetic purposes

All of the oil-soluble constituents are heated to 85° C. in a stirredvessel. When all of the constituents are molten, or are in the form of aliquid phase, the water phase is incorporated with homogenization. Whilebeing stirred, the emulsion is cooled to about 40° C., perfumed,homogenized and then cooled to 25° C. with continuous stirring.

Preparations Example 2

Composition for lip care ad 100 Eucerinum anhydricum 10.00  Glycerol10.00  Titanium dioxide 1.00 Compound of Example 1 8.00 Octylmethoxycinnamate 5.00 Zinc oxide 4.00 Castor oil 4.00 Pentaerythritylstearate/caprate/caprylate/adipate 3.00 Glyceryl stearate SE 2.00Beeswax 2.00 Microcrystalline wax 2.00 Quaternium-18 bentonite 1.50PEG-45/dodecyl glycol copolymer

Example 3

Composition for lip care ad 100 Eucerinum anhydricum 10.00  Glycerol10.00  Titanium dioxide 1.50 Compound of Example 1 8.00 Octylmethoxycinnamate 5.00 Zinc oxide 4.00 Castor oil 4.00 Pentaerythritylstearate/caprate/caprylate/adipate 3.00 Glyceryl stearate SE 2.00Beeswax 2.00 Microcrystalline wax 2.00 Quaternium-18 bentonite 1.50PEG-45/dodecyl glycol copolymer

Example 4

Composition for sunblock containing micropigments ad 100 Water 10.00 Octyl methoxycinnamate 6.00 PEG-7 hydrogenated castor oil 6.00 Titaniumdioxide 3.00 Compound of Example 1 5.00 Mineral oil 5.00 Isoamylp-methoxycinnamate 5.00 Propylene glycol 3.00 Jojoba oil 3.004-Methylbenzylidenecamphor 2.00 PEG-45/dodecyl glycol copolymer 1.00Dimethicone 0.50 PEG-40 hydrogenated castor oil 0.50 Tocopheryl acetate0.50 Phenoxyethanol 0.20 EDTA

Example 5

Composition for sunblock containing micropigments ad 100 Water 10.00 Octyl methoxycinnamate 6.00 PEG-7 hydrogenated castor oil 6.00 Titaniumdioxide 2.00 Compound of Example 1 5.00 Mineral oil 5.00 Isoamylp-methoxycinnamate 5.00 Propylene glycol 3.00 Jojoba oil 3.004-Methylbenzylidenecamphor 2.00 PEG-45/dodecyl glycol copolymer 1.00Dimethicone 0.50 PEG-40 hydrogenated castor oil 0.50 Tocopheryl acetate0.50 Phenoxyethanol 0.20 EDTA

Example 6

Grease-free gel ad 100 Water 8.00 Octyl methoxycinnamate 7.00 Titaniumdioxide 1.50 Compound of Example 1 5.00 Glycerol 5.00 PEG-25 PABA 1.004-Methylbenzylidenecamphor 0.40 Acrylate C₁₀-C₃₀ alkyl acrylatecrosspolymer 0.30 Imidazolidinylurea 0.25 Hydroxyethylcellulose 0.25Sodium methylparaben 0.20 Disodium EDTA 0.15 Fragrance 0.15 Sodiumpropylparaben 0.10 Sodium hydroxide

Example 7

Grease-free gel ad 100 Water 8.00 Octyl methoxycinnamate 7.00 Titaniumdioxide 2.00 Compound of Example 1 5.00 Glycerol 5.00 PEG-25 PABA 1.004-Methylbenzylidenecamphor 0.40 Acrylate C₁₀-C₃₀ alkyl acrylatecrosspolymer 0.30 Imidazolidinylurea 0.25 Hydroxyethylcellulose 0.25Sodium methylparaben 0.20 Disodium EDTA 0.15 Fragrance 0.15 Sodiumpropylparaben 0.10 Sodium hydroxide

Example 8

Sun cream ad 100 Water 8.00 Octyl methoxycinnamate 8.00 Titanium dioxide6.00 PEG-7 hydrogenated castor oil 1.00 Compound of Example 1 6.00Mineral oil 5.00 Zinc oxide 5.00 Isopropyl palmitate 5.00Imidazolidinylurea 3.00 Jojoba oil 2.00 PEG-45/dodecyl glycol copolymer1.00 4-Methylbenzylidenecamphor 0.60 Magnesium stearate 0.50 Tocopherylacetate 0.25 Methylparaben 0.20 Disodium EDTA 0.15 Propylparaben

Example 9

Sun cream ad 100 Water 8.00 Octyl methoxycinnamate 8.00 Titanium dioxide6.00 PEG-7 hydrogenated castor oil 1.00 Compound of the formula 1 6.00Mineral oil 5.00 Zinc oxide 5.00 Isopropyl palmitate 5.00Imidazolidinylurea 3.00 Jojoba oil 2.00 PEG-45/dodecyl glycol copolymer1.00 4-Methylbenzylidenecamphor 0.60 Magnesium stearate 0.50 Tocopherylacetate 0.25 Methylparaben 0.20 Disodium EDTA 0.15 Propylparaben

Example 10

Water-resistant sun cream ad 100 Water 8.00 Octyl methoxycinnamate 5.00PEG-7 hydrogenated castor oil 5.00 Propylene glycol 4.00 Isopropylpalmitate 4.00 Caprylic/capric triglyceride 1.50 Compound of the formula1 4.00 Glycerol 3.00 Jojoba oil 2.00 4-Methylbenzylidenecamphor 2.00Titanium dioxide 1.50 PEG-45/dodecyl glycol copolymer 1.50 Dimethicone0.70 Magnesium sulfate 0.50 Magnesium stearate 0.15 Fragrance

Example 11

Water-resistant sun cream ad 100 Water 8.00 Octyl methoxycinnamate 5.00PEG-7 hydrogenated castor oil 5.00 Propylene glycol 4.00 Isopropylpalmitate 4.00 Caprylic/capric triglyceride 1.00 Compound of the formula1 4.00 Glycerol 3.00 Jojoba oil 2.00 4-Methylbenzylidenecamphor 2.00Titanium dioxide 1.50 PEG-45/dodecyl glycol copolymer 1.50 Dimethicone0.70 Magnesium sulfate 0.50 Magnesium stearate 0.15 Fragrance

Example 12

Sun milk ad 100 Water 10.00  Mineral oil 6.00 PEG-7 hydrogenated castoroil 5.00 Isopropyl palmitate 3.50 Octyl methoxycinnamate 0.50 Compoundof Example 1 3.00 Caprylic/capric triglyceride 3.00 Jojoba oil 2.00PEG-45/dodecyl glycol copolymer 0.70 Magnesium sulfate 0.60 Magnesiumstearate 0.50 Tocopheryl acetate 0.30 Glycerol 0.25 Methylparaben 0.15Propylparaben 0.05 Tocopherol

Example 13

Sun milk ad 100 Water 10.00  Mineral oil 6.00 PEG-7 hydrogenated castoroil 5.00 Isopropyl palmitate 3.50 Octyl methoxycinnamate 0.50 Compoundof Example 1 3.00 Caprylic/capric triglyceride 3.00 Jojoba oil 2.00PEG-45/dodecyl glycol copolymer 0.70 Magnesium sulfate 0.60 Magnesiumstearate 0.50 Tocopheryl acetate 0.30 Glycerol 0.25 Methylparaben 0.15Propylparaben 0.05 Tocopherol

Example 14

Water-resistant sun cream ad 100 Water 8.00 Octyl methoxycinnamate 5.00PEG-7 hydrogenated castor oil 5.00 Propylene glycol 4.00 Isopropylpalmitate 4.00 Caprylic/capric triglyceride 2.00 Compound of Example 14.00 Glycerol 3.00 Jojoba oil 2.00 4-Methylbenzylidenecamphor 2.00Titanium dioxide 1.50 PEG-45/dodecyl glycol copolymer 1.50 Dimethicone0.70 Magnesium sulfate 0.50 Magnesium stearate 0.15 Fragrance

Example 15

Sun milk ad 100 Water 10.00  Mineral oil 6.00 PEG-7 hydrogenated castoroil 5.00 Isopropyl palmitate 3.50 Octyl methoxycinnamate 2.00 Compoundof Example 1 3.00 Caprylic/capric triglyceride 3.00 Jojoba oil 2.00PEG-45/dodecyl glycol copolymer 0.70 Magnesium sulfate 0.60 Magnesiumstearate 0.50 Tocopheryl acetate 0.30 Glycerol 0.25 Methylparaben 0.15Propylparaben 0.05 Tocopherol

1-8. (canceled)
 9. A tris(ethenylamino)triazine of the formula Ill

in which the radicals R¹ and R² are identical or different and are—COOR⁴, —COR⁴, —CON(R⁴)₂, —CN, —SO₂R⁴, —SO₂OR⁴ or —PO(OR⁴)₂, where theradicals R⁴, independently of one another, are hydrogen, an aliphatic,cycloaliphati8c, araliphatic or aromatic radical, each of which may beoptionally substituted, and where two adjacent radicals R may optionallyform a ring and R³ is hydrogen or an aliphatic, cycloaliphatic,araliphatic or aromatic radical, each of which may be substituted.